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Abstract
Increasing traffic loading and volumes on roads have led to the use of polymer modified binders to
improve the performance of bitumen in terms of strength, durability, and resistance to rutting.
This research studies the effect of adding poly methyl methacrylate (PMMA) with different mo-
lecular weights on asphalt properties. PMMA polymer was prepared via solution polymerization
of MMA using dibenzoyl peroxide (DBPO) as initiator. By controlling the time of reaction, two dif-
ferent molecular weights were obtained: PMMA1 and PMMA2 with Mw 21.000 and 30.000, respec-
tively. The morphological studies of polymer modified binder were discussed. Physical properties
of PMMA modified asphalt including penetration value, softening point, and kinematic viscosity at
135C and 150C were examined. The aging properties of polymer modified asphalts were exam-
ined using thin film oven test (TFOT). A hot storage stability test was carried out for polymer
modified binder. Indirect tensile strength (ITS) test and durability performance of modified as-
phalts were evaluated using Marshall Test. Resilient modulus (RM) test was evaluated using Uni-
versal Testing Machine. Results showed that the inclusion of PMMA polymer in asphalt binder has
significantly improved its properties. The achieved improvement was found to be dependent on
polymer molecular weight. Moreover, the results explained that the compatibility between PMMA
and asphalt binder is improved upon further aging especially with low molecular weight polymer
(PMMA).
Keywords
Asphalt Binder, Rutting, PMMA, TFOT, Ageing
*
Corresponding author.
How to cite this paper: Haggam, R.A., et al. (2014) Improvement of Asphalt Properties Using Polymethyl Methacrylate.
Open Journal of Organic Polymer Materials, 4, 43-54. http://dx.doi.org/10.4236/ojopm.2014.42007
R. A. Haggam et al.
1. Introduction
Traditionally, conventional binders, such as binder with 100 penetration grade (100 pen.) and 60 penetration
grades (60 pen.), were used in road pavement construction. However, increased axle loading, and braking power
of vehicles in recent years required the durability and strength of the binder to resist rutting, fatigue, and crack-
ing tendencies of road pavements. One means of achieving this is to modify the bitumen with polymers [1]. The
addition of polymers, chains of repeated small molecules, to asphalt has been shown to improve performance.
Pavement with polymer modification exhibits greater resistance to rutting and thermal cracking, and decreases
fatigue damage, stripping, and temperature susceptibility. Polymers that are used for asphalt modification can be
grouped into three main categories: thermoplastic elastomers, plastomers and reactive polymers. Thermoplastic
elastomers are obviously able to confer good elastic properties on thermomodified binder; while plastomers and
reactive polymers are added to improve rigidity, and reduce deformations under load. Belonging to the first
category, styrene-butadiene-styrene block (SBS) copolymers are probably the most frequently used asphalt
modifiers for paving applications [2]-[5]. Examples of the plastomeric types of polymers were studied since as-
phalt modifications are polyethylene (PE), and ethylene-butyl acrylate (EBA) random copolymers [6]-[9]. Due
to its low compatibility with asphalt, PE is not widely used for paving applications, and thus ethylene copoly-
mersare preferred. Recently, reactive polymers have been introduced as asphalt modifiers. Their reactivity is
due to the presence of functional groups supposedly able to bond with asphalt molecules. Polarity of the poly-
mer can enhance its solubility and compatibility with base bitumen. Polar groups present in the polymer mole-
cules can react with the polar constituents of bitumen. Subsequently, phase separation is prevented, which in
turn enhances the materials consistency, and decreases oxidative ageing [10]-[13]. Among polar polymers, a
very limited number of studies discuss the fundamental properties of modified bitumens with acrylate polymers.
Most frequently used acrylates as bitumen modifying agents in road applications are ethylene vinyl acetate
(EVA) glycidyl methacrylate (EA) terpolymer, ethylene butyl acrylate (EBA) copolymer, etc. [14]-[16]. In this
research, different molecular weights from PMMA were added to asphalt for improving the performance of bi-
tumen in terms of strength, durability, and resistance to rutting.
2. Experimental
Materials
Methyle methacrylate monomer (MMA) was supplied by Navol, Dibenzoylperoxide (DBPO) was obtained from
Merck, Toluene and methanol solvents were obtained from Carloerba reagents. Local asphalt of penetration
grade 60/70, produced by El-Nasser Petroleum Company, Suez-Egypt. The crushed Limestone aggregate, lime-
stone mineral filler, and crushed sand were originally obtained from Ataka Suez-Egypt. The physical properties
of the asphalt binder and the aggregate are given in Table 1 and Table 2, respectively. Aggregate gradation is
also provided in Table 3.
Properties Values
Physical properties:
-Penetration at 25C 100 g, 5 seconds, 0.1 mm 60
-Kinematics viscosity at 135C, C.st. 346
-Absolute viscosity at 60C, poise. 2122
-Flash point, C (Cleveland open cup) 250
-Ductility at 25C, 5 cm/min, cm +100
-Softening point C (Ring and Ball) 52
-Solubility in trichloroethylene, % 99.9
Chemical constituents
Oil fractions 26.2
Resins fractions 48.4
Asphaltenes fractions 25.4
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R. A. Haggam et al.
Ranged of Standards
Sieve size (mm) Passing (%) Retained (%)
25 0 0
19 82 - 100 9
12.5 68 - 87 13
9.5 60 - 79 8
4.75 46 - 65 14
2.36 34 - 51 13
0.425 17 - 29 20
0.180 9 - 18 9
0.075 2-7 9
Pan 0 5
3. Methods of Preparation
3.1. Solution Polymerization of Methyl Methacrylate [17]
Polymerization was performed in glass reactor (1000 mL) equipped with a mixing system and thermostated at
90C, using a monomer solution contained MMA (40%, wt/wt) and toluene solvent. After attaining constant
temperature, 0.5 wt% of (DBPO) was added. Two different molecular weights of PMMA polymers were ob-
tained by controlling the time of reaction since the termination reaction is time dependent [18]. In predetermined
intervals solution (5 mL) was removed, mixed with of methanol (100 mL) and after staying overnight at room
temperature, the precipitate was filtered off, washed with methanol, dried and weighed. Each experiment was
performed at least three times.
4. Testing Procedures
The principal test methods on the reheated modified blends and base asphalt include:
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R. A. Haggam et al.
cosity (C.st) at 135C and 150C according to ASTM D-2170 [21]. Thin Film Oven Test (TFOT): The procedure
according to ASTM D1754 [22] was developed to simulate the effect of heating in a hot-mix plant operation on
asphalt cement. In the standard TFOT procedure, the asphalt cement sample is poured into a flat-bottomed pan
to a depth of about 3.2 mm. The pan with the asphalt sample is then placed on a rotating shelf in an oven, and
kept at a temperature of 163C for 5 hrs. The properties of the asphalt before and after the TFOT procedure are
measured to determine the change in properties that might be expected after a hot-mix plant operation Table 4.
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R. A. Haggam et al.
tures. It is defined as the ratio of the repeated stress to the corresponding resilient strain. Since the recoverable
portion of the strain is measured in a resilient modulus test, the stiffness of the material can be related to the
modulus of elasticity of the asphalt mix and commonly used for mechanistic analysis [26]. Therefore, the resil-
ient modulus of both unmodified and modified asphalt mixes was studied at different temperatures for predicting
the mixture design and pavement performance. The total resilient modulus (ERT) is defined in Equation (2):
E RT =( RT + 0.27 ) tHT (The total resilient modulus (ERT) definition) (2)
where, P is the repeated load (N), RT the total resilient Poissons ratio (a value of normally 0.35 used), t is the
thickness of specimen (mm) and HT is the total recoverable horizontal deformation (mm).
The test was done on Universal Testing Machine according to ASTM D 4123-82 [27]. The test was conducted
by applying the compressive load at 5C, 25C, 35C and 45C for 7% polymer modified and unmodified asphalt
mixes. Three laboratory fabricated Marshall specimens were tested. Prior to testing, three dimensional axes were
marked on the specimen and height of the sample was determined. The specimens were conditioned for 24 hrs in
the environmental chamber at the given temperature and then subjected to repeated loading (pulse width of 100
mms, pulse repetition period of 3000 mms and test pulse count of five).
(b)
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R. A. Haggam et al.
Table 6. Effect of modifier type and modifier content on Marshall test results.
Mix No. Polymer content (%) Asphalt content (%) Stability (N) Flow (mm)
Control 0 5.2 8690 2.75
4 9750 2.98
5 10,020 3.12
PMMA1 6 5.5 10,600 3.30
7 11,120 3.41
8 11,255 3.50
4 8955 2.78
5 9250 2.82
PMMA2 6 5.5 9620 2.90
7 9935 3.02
8 10,050 3.12
compacted mix under loads. According to these results, the flow value increased with increasing the polymer
percent added to with control binder. The percentage of flow value increases ranged between 8% and 24% with
the addition of 4% to 7% of PMMA1 respectively compared with the control mixture.
5.3. Penetration
Figure 2 shows the variation of penetration values with the various percentages of polymers added to asphalt.
The figure indicates that the penetration value decreases as the polymer content increases in the mixture. Reduc-
tion in penetration value ranges from 11% to 37% with the addition of 4%, and 7% of PMMA1, respectively,
while it ranges from 6.6% to 23% with the addition of 4% and 7% of PMMA2, respectively, compared to the
original asphalt. Furthermore, results indicated that no significant difference between 7% and 8% of polymer
content. This means that the addition of polymer makes the modified asphalt harder and more consistent, which
might improve the rutting resistance of the mixture, but on the other hand, it might affect flexibility of the bitu-
men by making the asphalt much stiffer, and thus the resistance to fatigue cracking can be affected.
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R. A. Haggam et al.
80
Control
70
1Binder
60 2Binder
Penetration 0.1 mm
50
40
30
20
10
0
Control 4 5 6 7 8
Polymer content %
100
90 Control
1Binder
80
Softening temperature C
2Binder
70
60
50
40
30
20
10
0
Control 4 5 6 7 8
Polymer content %
results that with the increase of molecular weight of polymer added to asphalt, the softening point value de-
creases, and also as the polymer content increases, the softening point increases. This increase ranges from 11C
to 18C with the addition of 4% to 7% of PMMA1, respectively, while it ranges from 5C to 13C with the addi-
tion of 4% to 7% of PMMA2, respectively. This phenomenon indicates that the resistance of the binder to the
effect of heat is increased and it will reduce its tendency to soften in hot weather. Thus with the addition of
polymer, the modified binder will be less susceptible to temperature changes.
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R. A. Haggam et al.
1200
Control
1000 1Binder
Kinematic viscosity, C.st
2Binder
800
600
400
200
0
Control 4 5 6 7 8
Polymer content %
700
Control
600
1Binder
Kinematic viscosity, C.st
500 2Binder
400
300
200
100
0
Control 4 5 6 7 8
Polymer content %
50
R. A. Haggam et al.
14000
Control
12000 1Mix
2Mix
10000
Stability (N)
8000
6000
4000
2000
0
Control 4 5 6 7 8
Polymer content %
5.10. Rutting
As shown in Table 8, a significant improvement in rutting depth (permanent deformation) was observed for the
modified mixes compared to the control mixture. The percentage of decrease ranged between 44% and 65% for
mixture2 and mixture1, respectively, compared to control mix. It is important to note that the percentage of im-
provement for mixture1 is higher than mixture2. This might be due to the good mechanical properties of
PMMA1.
6. Conclusion
In this investigation, both physical and mechanical characteristics of the control and asphalt mixtures in terms of
penetration, softening point, kinematic viscosities and stability were evaluated. The indirect tensile strength, re-
silient modulus and permanent deformation were studied as well. A notable achievement for the examined
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R. A. Haggam et al.
16
Dry Wet
14
12
ITS (kg/sq.cm
10
0
Control mix PMMA1 PMMA2
Mix types
4500
Unmodified mix Modified mix
4000
3500
Resilient modulus MPa
3000
2500
2000
1500
1000
500
0
5C 25C 35C 45C
Temperature C
Table 7. Effect of TFOT on physical properties of unmodified and modified asphalt cement 60/70.
4 0.16 53 79
5 0.15 48 82
PMMA1 6 0.12 44 86
7 0.10 38 89
8 0.08 37 89
4 0.18 56 73
5 0.17 52 74
PMMA2 6 0.15 50 76
7 0.14 46 80
8 0.12 45 80
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R. A. Haggam et al.
0 0 0 0 0
5 210 0.0427 0.0080 0.0191
10 420 0.0826 0.0200 0.0311
15 630 0.1022 0.0308 0.0502
20 840 0.1305 0.0333 0.0639
25 1050 0.1665 0.0453 0.0849
30 1260 0.1903 0.0635 0.1006
35 1470 0.2153 0.0730 0.1117
40 1680 0.2211 0.0790 0.1168
45 1890 0.2303 0.0802 0.1289
50 2100 0.2305 0.0810 0.1290
55 2310 0.2305 0.0810 0.1290
60 2520 0.2305 0.0810 0.1290
Mix1: control binder with PMMA1, Mix2: control binder with PMMA2.
properties was observed such as a good compatibility of the polymers with the base bitumen especially PMMA1,
increasing the softening point and decreasing penetration and viscosity. In addition the stability and tensile
strength increase with increasing the PMMA1 percent. The asphalt binder with PMMA1 shows the best im-
provement after TFOT ageing. And finally, significant improvement in permanent deformation was observed for
the modified mixtures with PMMA1compared to the control mixture.
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